Product of the reductive alkylation of 1, 3-diamino-2-propanol and a ketone



United States Patent 3,189,613 PRODUCT OF THE REDUCTIVE ALKYLATION 0F1,3-DIANHNO-2-PROPANOL AND A KETONE Henryk A. Cyba, Chicago, 11].,assiguor to Universal Oil Products Company, Des Plaines, 11]., acorporation of Delaware No Drawing. Filed Apr. 9, 1962, Ser. No. 185,8447 Claims. (Cl. 260-307) This application is a continuation-in-part of mycopending application, Serial No. 130,238, filed August 9, 1961, which,in turn, is a continuation-in-part of now abandoned application, SerialNo. 647,190, filed March 20, 1957, and relates to a novel composition ofmatter.

The novel composition of matter of the present invention possessesutility as an additive for the stabilization of organic compounds andalso may possess utility as an intermediate in the preparation ofcomplex chemical compounds.

The compound of the present invention is advantageous for use as anadditive in hydrocarbon distillates and serves to improve thehydrocarbon distillate in a number of different ways. For example, infuel oils, burner oils, range oils, diesel oils, marine oils, turbineoils, cutting oils, rolling oils, soluble oils, drawing oils, slushiugoils, slushing greases, lubricating oils, lubricating greases,fingerprint removers, etc., the distillate or grease is improved in oneor more ways including retarding sediment formation, dispersion ofsediment when formed, retarding discoloration, oxidation inhibitor, rustor corrosion inhibitor, detergent, etc. In lubricating type oils, inaddition to all or some of the properties hereinbefore set forth, theadditive may function as a pour point depressant, viscosity indeximprover, anti-foaming agent, etc. In liquefied petroleum gases,gasoline, naphtha, aromatic solvents, kerosene, jet fuels, etc., theadditive serves as a corrosion inhibitor along with one or more of theother functions mentioned above. In gasoline the product also functionsas antior de-icing additive, carburetor detergent, etc. In other organiccompounds, including alcohols, ethers, chlorinated hydrocarbons,synthetic diand polyesters such as dioctyl sebacate, dioctyl adipate,tn'methylolpropane tripelargonate, trimethylolpropane tricaproate,trimethylolpropane tricaprylate, etc., and com positions containingthem, glyceridic oils and fats, waxes, other oils and fats of animal orvegetable origin, etc., the additive functions as a beneficent in one ormore of the manners herein set forth or otherwise.

The novel composition of matter of the present invention is particularlyapplicable to the stabilization of hydrocarbon distillates heavier thangasoline. The hydrocarbon distillate may be cracked, straight run ormixtures thereof. Many burner oils and particularly blends of straightrun and cracked fuel oils undergo deterioration in storage, resulting inthe formation of sediment, discoloration, etc. The formation of sedimentis objectionable because the sediment tends to plug burner tips,injectors, etc. In jet fuels, oil-fuel heat exchangers and burnernozzles are plugged. In diesel fuel, the deterioration tends to formvarnish and sludge in the diesel engine. Discoloration of burner oils isobjectionable for various reasons, including customers preference forlight colored oils.

In handling of hydrocarbon distillates and other organic liquids, it isoften necessary to transport and/or store such materials in metalcontainers, as in steel or other metal pipe lines, drums, tanks, etc.Since these materials often contain varying amounts of water in solutionor in suspension which may separate, due to temperature changes,internal corrosion of the container by separating water almostinvariably occurs to a greater or lesser degree. The water thusseparated forms as a film or in minute droplets in the pipe line or onthe container walls or even in small pools at the bottom of thecontainer. This brings about ideal conditions for corrosion andconsequent damage to the metal surfaces of the container, as well as theserious contamination of the hydrocarbon oil or other materialscontained therein by the corrosion products.

Corrosion problems also occur, for example, in the lubrication ofinternal combustion engines or steam engines, including turbines andother similar machinery, in which a quantity of water is often observedas a separate phase within the lubricating system as a result of thecondensation of water from the atmosphere or, in the case of internalcombustion engines, as the result of dispersion or absorption inlubricating oil of water formed as a product of fuel combustion. Waterin such instances corrodes the various metal parts of the machinery withwhich it comes into contact, the corrosion products causing furthermechanical damage to bearing surfaces and the like due to their abrasivenature and catalytically promoting the chemical degradation of thelubricant. Corrosion problems also arise in the preparation,transportation and use of various coating compositions such as greases,household oils, paints, lacquer, etc., which often are applied to metalsurfaces for protective purposes.

In one embodiment the present invention relates to the product resultingfrom the reductive alkylation of 1,3- diamino-Z-propanol with a ketoneselected from the group consisting of aliphatic ketones andcycloaliphatic ketones.

In a specific embodiment the present invention relates to the productresulting from the reductive alkylation of 1,3-diamino-2-propanol withmethyl heptadecyl ketone.

For use as an additive for the stabilization of organic substrates andespecially for the stabilization of hydrocarbon oils, the ketone used inthe reductive alkylation contains at least 8 carbon atoms. As will beshown by the data in the appended examples, the additive prepared byreductive alkylation of 1,3-diamino-2-propanol with an aliphatic ketonehaving at least 8 carbon atoms possesses unexpected and superiorproperties for such use. The peculiar properties of these reductivealkylation products are surprising when compared with the reactionproducts prepared from aryl alkyl ketones or various other aminocompounds. Normally, it would be expected that the reaction products ofthese other amino compounds with ketones or those prepared from arylketones would possess substantially equivalent properties as inhibitors,and it is surprising to find that the reaction products prepared from1,3-diamino-2-propanol and aliphatic ketones of more than 8 carbon atomspossess the considerably superior properties as illustrated in theexamples of the present application.

As hereinbefore set forth, when used as an additive for hydrocarbondistillates, the composition of the present invention is prepared by thereductive alkylation of 1,3- diamino-Z-propanol with an aliphatic ketonehaving at least 8 and preferably as least 12 carbon atoms. For such use,it is essential that the ketone contains at least 8 carbon atoms andpreferably at least 12 carbon atoms and usually the ketone will containfrom about 8 and preferably from about 12 to about 50 carbon atoms permolecule.

Any suitable aliphatic ketone may be employed. Illustrative ketonescontaining at least 12 carbon atoms include methyl decyl ketone, methylundecyl ketone, methyl dodecyl ketone, methyl tridecyl ketone, methyltetradecyl ketone, methyl pentadecyl ketone, methyl hexadecyl ketone,methyl heptadecyl ketone, methyl octadecyl ketone, methyl nonadecylketone, methyl eicosyl ketone, methyl heneicosyl ketone, methyl docosylketone, methyl tricosyl ketone, methyl tetracosyl ketone, methylpentacosyl ketone, methyl hexacosyl ketone, methyl heptacosyl ketone,

methyl octacosyl ketone, methyl nonacosyl ketone, methyl triacontylketone, etc., ethyl nonyl ketone, ethyl decyl ketone, ethyl undecylketone, ethyl dodecyl ketone, ethyl tridecyl ketone, ethyl tetradecylketone, ethyl pentadecyl ketone, ethyl hexadecyl ketone, ethylheptadecyl ketone, ethyl octadecyl ketone, ethyl nonadecyl ketone, ethyleicosyl ketone, ethyl heneicosyl ketone, ethyl docosyl ketone, ethyltricosyl ketone, ethyl tetracosyl ketone, ethyl pentacosyl ketone, ethylhexacosyl ketone, ethyl heptacosyl ketone, ethyl octacosyl ketone, ethylnonacosyl ketone, ethyl triacontyl ketone, etc., propyl octyl ketone,propyl nonyl ketone, propyl decyl ketone, propyl undecyl ketone, propyldodecyl ketone, propyl tridecyl ketone, propyl tetradecyl ketone, propylpentadecyl ketone, propyl hexadecyl ketone, propyl heptadecyl ketone,propyl octadecyl ketone, propyl nonadecyl ketone, propyl eicosyl ketone,propyl heneicosyl ketone, propyl docosyl ketone, propyl tricosyl ketone,propyl tetracosyl ketone, propyl pentacosyl ketone, propyl hexacosylketone, propyl heptacosyl ketone, propyl octacosyl ketone, propylnonacosyl ketone, propyl triacontyl ketone, etc., butyl heptyl ketone,butyl octyl ketone, butyl nonyl ketone, butyl decyl ketone, butylundecyl ketone, butyl dodecyl ketone, butyl tridecyl ketone, butyltetradecyl ketone, butyl pentadecyl ketone, butyl hexadecyl ketone,butyl heptadecyl ketone, butyl octadecyl ketone, butyl nonadecyl ketone,butyl eicosyl ketone, butyl heneicosyl ketone, butyl docosyl ketone,butyl tricosyl ketone, butyl tetracosyl ketone, butyl pentacosyl ketone,butyl hexacosyl ketone, butyl heptacosyl ketone, butyl octacosyl ketone,butyl nonacosyl ketone, butyl triacontyl ketone, etc.

A number of ketones containing at least 12 carbon atoms are available asmixtures which are either products or by-products of commercialoperations. These mixtures generally are available at comparatively lowcost and, as another advantage of the present invention, the mixturesmay be used without the added time and expense of separating specificcompounds in pure state. One such mixture available commercially as aprimary product of the process is Stearone, which is diheptadecylketone. Another such mixture is Laurone, which is dilauryl ketone.

As hereinbefore set forth in another embodiment of the invention, theketone may contain at least 8 carbon atoms. Illustrative ketonescontaining from 8 to 11 carbon atoms include methyl hexyl ketone, methylheptyl ketone, methyl octyl ketone, methyl nonyl ketone, ethyl amylketone, ethyl hexyl ketone, ethyl heptyl ketone, ethyl octyl ketone,propyl butyl ketone, propyl amyl ketone, propyl hex yl ketone, propylheptyl ketone, dibutyl ketone, butyl amyl ketone, butyl hexyl ketone,etc.

While the alkyl ketones are preferred, in some cases ketones containingunsaturation in the aliphatic group may be employed, but not necessarilywith equivalent results. Furthermore, while it generally is preferred toutilize the same ketone in forming the di-substituted product, it isunderstood, in some cases, that different ketones may be employed, atleast one and preferably both of the ketones containing at least 12carbon atoms each. In this embodiment one ketone preferably is reactedfirst with 1,3- diamino-Z-propanol and then the other ketone is reactedwith the product of the first reaction, either in the same reaction zoneor after removal of the first reaction product from the reaction zone.In some cases, the aliphatic ketone may contain a non-hydrocarbonsubstituent in the chain and this substituent may contain oxygen,nitrogen, sulfur, etc.

When the reduction 'alkylation product is used for other purposes, suchas the following intermediates in the preparation of complex chemicalcompounds including insecticides, plasticizers, acid gas absorbers, pHcontrol agents, curing agents for epoxide resins, cross-linking agentsfor polyurethane foams, emulsifiers, solubilizing agents, etc., theketone employed in the reductive alkylation may contain less than 8carbon atoms and, thus, Will be selected from acetone, methyl ethylketone, methyl propyl ketone,

methyl butyl ketone, methyl pentyl ketone, diethyl ketone, ethyl propylketone and dipropyl ketone. In still another embodiment the ketone usedin the reductive alkylation is a cycloaliphatic ketone and is selectedfrom cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone,cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone,cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecanone,cyclopentadecanone (Exaltone), cyclohexadecanone, cycloheptadecanone(dihydrocivetone), etc. It is understood that the reductive alkylationproducts prepared fromthese different ketones are not necessarilyequivalent for the same uses, but will posses utility for other uses as,for example, the specific applications hereinbefore set forth.

The reaction of 1,3-diamino-2-propanol and ketone is etfected in anysuitable manner. In one embodiment the diamino propanol and ketone arereacted by heating at refluxing conditions. This results in thepreparation of a Schifi base and the Schiif base then is reduced in anysuitable manner and, particularly, by hydrogenating in the presence ofhydrogen and a hydrogenation catalyst including nickel, platinum,palladium, etc., the hydrogenation generally being effected at atemperature of from about atmospheric to about 200 C., although highertemperatures may be employed in some cases. In still another embodiment,the reaction of 1,3-diamino-2- propanol and ketone may be effected inthe presence of hydrogen and a hydrogenation catalyst in order to formthe reductively alkylated product in one step.

When desired, the reaction is eifected in the presence of a solvent. Anysuitable solvent may be employed and preferably comprises a hydrocarbonincluding benzene, toluene, xylene, ethyl benzene, cumene, decalin,naphtha, etc. The temperature of reaction will depend upon whether asolvent is employed and, when employed, upon the particular solvent. Ingeneral, the reaction is effected at a temperature of from about toabout 200 C. Water formed during the reaction may be removed in anysuitable manner including, for example, by separating under reducedpressure, by removing an azeotrope of water-solvent, by distilling thereaction product at an elevated temperature, etc.

It will be noted that 1,3-diamino-2-propanol contains two primary aminogroups (NH groups) and that the reaction product may comprise themonoand/ or di-substituted diamino propanol. Generally, thedi-substituted product is obtained, although the mono-substituted or amixture of the monoand di-substituted product may be prepared andutilized in the present invention. When the mono-substituted product isdesired, one mol of ketone is reacted per mol of diamino propanol. Whenthe di-subtituted product is desired, two mols of ketone are reacted permol of the diamino propanol. In order to insure complete reaction, it isunderstood that an excess of the diamino alcohol or ketone may besupplied to the reaction zone, and the excess preferably is subsequentlyremoved in any suitable manner.

It is believed that the reductive alkylation products of the presentinvention comprises compounds having one or more chemical structuresillustrated by structures (1) and (2) below.

a r r H R(IJNCCIJ-('J-IITH R Li 0-1-1 H H H H H H H II I I I I I I gR-(IJN(IJC-(IJN I R R H (La H n 2 R in the above structures representsthe residual aliphatic radicals derived from the ketone and will be thesame or diiferent composition and/or configuration depending upon theketone used as the reactant. However, cyclization may occur during thereaction and the com- ,5. position of the present invention may comprisecompounds of the general structure illustrated in structure (3).

Here again, R represents the aliphatic radicals derived from the ketone.

It is understood that the composition of the present invention willcomprise one of the compounds illustrated in the above structures or amixture of two or more thereof.

From the above description, it will be noted that a number of diiferentcompounds may be prepared and utilized in accordance with the presentinvention. As hereinbefore set forth, these compounds are notnecessarily equivalent for the same use, but will possess utility forother desired uses.

As hereinbefore set forth, the reductive alkylation products prepared inthe above manner are novel compositions of matter and, when preparedfrom alkyl ketones containing at least 8 carbon atoms, possessunexpected properties over related but different compositions of matterof the prior art. Depending upon the reactants and conditions employed,the reaction product may comprise a specific compound, but generallywill comprise a mixture of diiferent compounds. Another advantage to thepresent invention is that the mixture of compounds prepared in the abovemanner may be utilized without the added expense and time of separatinga specific compound from the mixture. The reaction products will rangefrom liquids to solids and, when desired, may be prepared as solutionsin suitable solvents for ease of handling and use.

The reaction product is recovered as a viscous liquid or solid. In somecases, the product will be marketed and utilized as a solution in asolvent. Conveniently, this solvent comprises the same solvent used inpreparing the reaction product and is recovered in admixture with atleast a portion of the solvent, thereby avoiding the necessity ofremoving all of the solvent and subsequently adding it back. When a moredilute solution is desired than is recovered in the manner hereinbeforeset forth, it is understood that the same or different solvent may becommingled with the mixture to form a solution of the desiredconcentration.

The concentration of additive to be used in the organic substrate willdepend upon the particular substrate and the particular benefitsdesired. In one embodiment the additive will be used in a concentrationof from about 0.000l% to about 10% or more and, more specifically, in aconcentration of from about 0.001% to about 5% by weight of thesubstrate. In most cases the additive will be used in a concentration offrom about 0.001% to about 1% by weight of the substrate.

It is understood that the additive of the present invention may be usedalong with other additives incorporated in the substrate including, forexample, higher alcohols, esters, organic amines, polybutene, sulfurizedfatty materials, sulfur-chlorine compounds, dyes, fillers, etc. In somecases it may be of advantage to also include a metal deactivator as, forexample, disalicylal diaminopropane, etc., or to include other additivessuch as tricresyl phosphate, dialkylphenols, trialkylphenols, including2,6-ditert-butyl-4-methylphenol, 2,4-methyl-6-tert-butylphenol,dialkylphenylene diamines, diarylphenylene diamines, diarnino diphenylmethanes, tetraalkyl diaminodiphenyl methanes, diphenylamine, alkylateddiphenylamine, styrenated diphenylamine, aminophenols, alkylaminophenols, phenothiazine, organic selenium compounds, zincdialkyldithiocarbamates, cadmium dialkyldithiocarbamates, naphthols,hydroxydiphenylamines, naphthyl-pphenylene diamine,phenyl-alpha-naphthylamine, phenylbeta-naphthylamine, alkoxydiphenylamine, N-phenyl-N'- cyclohexyl-p-phenylene diamine, reactionproducts of sulfur dichloride or sulfur monochloride with alkylphenols,aniline, alkylanilines, reaction products of formaldehyde andalkylphenols, guaiacol, etc.

In other cases, especially in lubricating oils, the additive of thepresent invention may be used in combination with one or more of bearingcorrosion inhibitors, peroxide decomposers or antioxidants: zincdialkyldithiophosphates, phosphorus pentasulfide-olefin reactionproducts, sulfur-olefin reaction products, sulfurized terpenes, aromatichydroxysulfides and disulfides and their neutralization products withcalcium, barium and magnesium oxides or hydroxides, calcium, barium ormagnesium sulfonates, barium or calcium alkylphenates, etc., as well asadditional corrosion inhibitors, extreme pressure additives, viscosityindex improvers, detergents, etc. When desired, the inhibitorcomposition of the present invention may be prepared as a mixture withone or more of these other additives and incorporated in the substratein this manner.

The additive may be incorporated in the substrate in any suitablemanner. As hereinbefore set forth, the additive conveniently is marketedas a solution in a suitable solvent, including hydrocarbons andparticularly aromatic hydrocarbons as benzene, toluene, xylene, cumene,etc. When the additive is to be incorporated in a liquid substrate, itmay be added thereto in the desired amount and the resultant mixturesuitable agitated in order to obtain intimate admixing of the additivein the substrate. When the additive is to be utilized as a corrosioninhibitor in plant equipment, it may be introduced into a fractionator,vapor line or at any other suitable point in order to prevent corrosionof the plant equipment. In this embodiment, the additive carries overinto the product of the process and also serves therein as abeneficient. It is understood that a portion of the additive may beintroduced into the plant equipment and an additional portion of theadditive incorporated in the effluent product when so desired.

The following examples are introduced to illustrate further the noveltyand utility of the present invention but not with the intention ofunduly limiting the same.

EXAMPLE I The product of this example was prepared by the reductivealkylation of 1,3-diamino-2-propanol with methyl heptadecyl ketone. 45g. of 1,3-diamino-2-propanol (0.5 mo1+5 g. excess) was refluxed with 282g. of methyl heptadecyl ketone (1 mol) in 200 g. toluene. 20.8 cc. ofwater was collected. The product then was reduced by hydrogenating at C.in the presence of a platinum-containing catalyst. The basic molcombining weight found by titration with 0.1 N perchloric acid inglacial acetic acid-benzene was 327, the calculated for thedisubstituted compound being 311. The product is a white powder, meltingat 6l63 C. and has a specific gravity at F. of 0.8584.

The reductive alkylation product prepared in the above manner was testedin a method referred to as the Erdco test. In this method, heated oil ispassed through a filter, and the time required to develop a differentialpressure across the filter of 25 in. Hg is determined. It is apparentthat the longer the time, the more effective is the additive. However,with a very effective additive, the time to reach a diiferentialpressure across the filter of 25 in. Hg is lengthened beyond reasonablelimits so that the test is stopped after about 300 minutes and thedifferential pressure at that time is reported.

0.001% by weight of the reaction product prepared in the above mannerwas incorporated in a commercial range oil and run in the Erdco test.After 300 minutes the differential pressure across the filter was 0.8in. Hg. On the other hand, a control sample (not containing thisadditive) developed a differential pressure across the filter of 25 in.Hg in 120 minutes. In still another test, 0.0005% of the same additivegave a differential pressure across the filter of 1.1 in. Hg after 300minutes.

It will be noted that the additive of the present invention served toconsiderably retard deterioration of the range oil and thus will preventclogging of burner tips, injectors, etc. during use of the oil.

EXAMPLE II Deterioration of burner oil also is evidenced bydiscoloration. In this example, a commercial fuel oil was stored for.about 164 days at 100 F. and the color of the oil was determined aftersuch storage. The color was determined in a Lumetron, Model 402-E,spectrophotometer. In this determination, the lower the number, thedarker is the oil.

The additive used in this example was prepared by the reaction of1,3-diamino-2-propanol with stearone, which is diheptadecyl ketone. 22.5g. of 1,3-diamino-2-propanol (0.25 mol+2.5 g. excess) was refluxed with269 g. stearone (0.5 mol) in 200 g. of toluene. 10 cc. of water wascollected. The product was reduced with hydrogen at 140 C. in thepresence of a platinum-containing catalyst. The toluene solvent wasevaporated by distilling under vacuum on a steam bath. The reactionproduct is a snow-white powder. Crystallized from Formula 30 alcohol, itmelts at 727 5 C. The specific gravity at 155 F. is 0.8506.

0.01% of the reaction product prepared in the above manner wasincorporated in a sample of a commercial fuel oil and, after storage at100 F. for 165 days, the fuel oil had a color of 18. On the other hand,a control sample (not containing this additive) of the same oil afterstorage for 164 days at 100 F. had a color of 11. It will be noted thatthe reaction product of the present invention served to retarddiscoloration of the oil during storage.

EXAMPLE III Another method of evaluating the additive is to store thesame at 100 F. for a given time and then determine :the amount ofsediment formed during such storage. In this example, 0.01% by weight ofthe additive prepared as described in Example I was incorporated in asample of a commercial fuel oil. After 44 days storage at 100 1 the oilcontaining the additive had a sediment content of 0.5 mg. per 100 ml. Onthe other hand, a control sample of the same oil (not containing thisadditive) had a sediment content of 8.7 mg. per 100 ml. after storag at100 F. for 43 days. Here again, it will be noted that the additiveserved to considerably improve the burner oil.

EXAMPLE IV As hereinbefore set forth, the additive of the presentinvention also functions to retard corrosion. This was evaluated in ahumidity cabinet test. In this test, a highly polished steel panel isdipped into a viscous naphthenic mineral oil, excess oil is drained, andthe panel is placed in a humidity cabinet maintained at 120 F. in anatmosphere saturated with water. The panels are slowly rotated, and thedays required for visible corrosion to appear on the panel is reported.A panel dipped in a control sample of the oil (not containing thisadditive) undergoes visible corrosion in 2-3 hours.

One percent by weight of the additive prepared as described in Example Iwas incorporated in another sample of the oil. The pahel dipped in thisoil and then placed in the humidity cabinet did not undergo visiblecorrosion until after 9 days of exposure at 120 F. to the atmospheresaturated with water. Thus, it will be seen that the additive served toconsiderably reduce corrosion.

EXAMPLE V As hereinbefore set forth, the reaction product of 1,3-diamino-Z-propanol with an aliphatic ketone containing at least 8 carbonatoms possess unexpectedly superior properties for use as an additive tohydrocarbon distillates as compared with the reaction product of variousother amino compounds with ketones. For example, an additive heretoforeproposed for use in hydrocarbon distillates is prepared by the reactionof 2-hydroxy-acetophenone with 1,3-diamino-2-propanol. For comparativepurposes this reaction product was evaluated in the Erdco methoddescribed above.

The reaction product of 1,3-diamino-2-propanol with2-hydroxy-acetophenone was incorporated in a com-mercial JP-6 jet fuelin a concentration of 0.02% by weight. However, this additive was notcompletely soluble at this concentration in the jet fuel. Accordingly,it was necessary .to filter the jet fuel to remove sludge, water orextraneous impurities prior to the evaluation in the Erdco test.

The results of the evaluations in the Erdco test are reported in thefollowing table. This table also reports the results of an run made inthe same JP-6 jet fuel using the reaction product of Example I in orderto compare these From the data in the above table it is seen that thereaction product of the present invention (reaction product of ExampleI) developed no pressure after 300 min utes. In contrast, the Schifisbase of 1,3-diamino-2-propanel with 2-hydroxy acetophenone developed adifierential pressure of 25 in. Hg within 52 minutes.

The above data confirm the criticality of the inhibitor of the presentinvention in requiring the use of an aliphatic ketone in preparing theinhibitor in contrast to the cyclic ketone illustrated by acetophenone.

EXAMPLE VI This example reports a comparison when using various ketonesin the reaction with 1,3-diamino-2-propanol. The evaluation reported inthe following table were made in the Erdco test hereinbefore describedand in the same JP-6 jet fuel as used in Example V.

Table 11 Diner ential Pressure, in. Hg

Additive Minutes None 0.02% by weight of the reaction product of ExampleI 0.02% by weight of the reductive alkylation product of1,3-diamino-2-propanol with ethyl amyl ketone 0.02% by weight of thereductive alkylation product of 1,3-diamino-2-propanol with methyl ethylketone The above data further demonstrate the requirement that theketone used in the preparation of the inhibitor of the present inventionmust contain at least 8 and preferably at least 12 carbon atoms permolecule. It will be noted that the reaction product with methyl ethylketone (4 carbon atoms) developed a differential pressure of 25 in. Hgin 32 minutes. In contrast, the reaction product of Example I developedno differential pressure after 300 minutes.

The reaction product using ethyl amyl ketone (8 carbon atoms) developeda differential pressure of 21 in.

Hg in 300 minutes. While this considerably improved as compared to theresults obtained with the reaction product using methyl ethyl ketone, itis not as good as the results obtained when using the reaction productprepared from methyl heptadecyl ketone (reaction product of Example I).Accordingly, for such use it is preferred that the ketone contains atleast 12 carbon atoms.

EXAMPLE VII Another important criterion in evaluating additives forhydrocarbon distillates in the Erdco test is the rating of the preheatertube. This rating is determined according to a CRC scale and reports thecondition of the tube in each 1 inch increment. The total length of thetube is 13 inches. The tube ratings for some of the runs reported inTables I and 11 above are shown in Table III below. The rating scale isas follows:

-No visible deposit 1Visible haze or dulling but no visible color2--Discoloration barely visible 3Light tan to peacock stain From thedata in the above table it will be seen that all 13 inches of the tubewere rated 0 (no visible deposit) for the run made with the reactionproduct of the present invention. In contrast, the control sample andthe runs with the other reaction products all showed a rating of 4 forthe first 6 inches of the tube. The tube cleanliness is an importantevaluation because the build-up of deposits in the tube eventually willplug the tube and interfere with satisfactory operation of theequipment.

EXAMPLE VIII As hereinbefore set forth, the use of 1,3-diamino-2-propanol with ketones having at least 8 carbon atoms is unique andsurprisingly superior to the reaction product of other amino compounds.The present example compares the results when using ethanol amine as areactant instead of 1,3-diamino-2-propanol. Normally, it would beexpected that the reductively alkylated products of these alkanol amineswould be substantially equivalent.

However, as shown by the data in the following table, theresults areconsiderably difierent.

These runs were made according to the Erdco method hereinbeforedescribed and using a commercial range oil similar to but ditierent fromthat used in Example I.

Table IV Additive tial Minutes Pres ure,

in. Hg

Nnne

0.001% by weight of the reductive alkylation product of1,3-diamino-2-propanol with methyl heptadecyl ketone (reaction productof Example I) 0.001% by weight of the reductive alkylation product of1,3-diamino-2-pr0panol with stearone (reaction product of Example II)0.01% by weight of the reductive alkylation product of ethanol aminewith methyl pentadecyl ketone 0.01% by weight of the reductivealkylation product of ethanol amlne with Laurone (dilauryl ketone)0.001% by weight of the reductive alkylation product of ethanol aminewith stearone From the data in the above table it is seen that the useof ethanol amine is not equivalent to the use of 1,3-diamino propanol inthe preparation of the inhibitor. It is to be noted that the reductivealkylation product prepared from 1,3-diamino-2-propanol developed verylow differential pressures after 300 minutes when used in the lowconcentration of 0.001% by weight. In contrast, the reductive alkylationproducts prepared from ethanol amine developed 25 in. Hg dilferentialpressure in less than 300 minutes, even when the additive was used in aconcentration of 0.01% by weight which is 10 times greater than the0.001% used with the inhibitors of the present invention.

EXAMPLE IX As hereinbefore set forth, the reductive alkylation productof the present invention possesses unexpectedly superior properites ascompared to the reductive alkylation product prepared from alkylenepolyamines. Tetraethylene pentamine is representative of the alkylenepolyamines heretofore proposed for reaction with ketones to prepareadditives for organic substances. The following table reports resultsusing the reductive alkylation product of tetraethylene pentamine withmethyl pentadecyl ketone and also the reductive alkylation product oftetraethylene pentamine with methyl heptadecyl ketone. Also included inthe following table are the results when using the reductive alkylationproduct of ethanol amine with methyl pentadecyl ketone.

These additives were used in a concentration of 0.001% in a blendedburner oil comprising commercial fuel oil and 15% cracked gasoline.

0.001% by weight of the reductive alkylation product of tetraethylenepentamine with methyl heptadecyl ketone 0.001% by weight of thereductive alkylation product of ethanol mine with methyl pentadecylketone From the data in the above table it will be noted that the oilsamples containing the reductive alkylation products prepared fromtetraethylene pentamine or ethanol amine all reached a differentialpressure of 25 in. Hg in less than minutes. In contrast, the oilcontaining the reductive alkylation product of the present inventiondoes not develop a differential pressure of in excess of 1 in. Hg after180 minutes.

I claim as my invention:

1. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with a ketone selected from the group consistingof aliphatic ketones and cycloaliphatic ketones in the presence ofhydrogen and a hydrogenation catalyst at a temperature of from aboutatmospheric to about 200 C.

2. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with an aliphatic ketone having from 3 to about50 carbon atoms in the presence of hydrogen and a hydrogenation catalystat a temperature of from about atmospheric to about 200 C.

3. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with an alkyl ketone having at least 8 carbonatoms in the presence of hydrogen and a hydrogenation catalyst at atemperature of from about atmospheric to about 200 C.

4. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with methyl heptadecyl ketone in the presence ofhydrogen and a hydrogenation catalyst 1 1 at a temperature of from aboutatmospheric to about 200 C.

5. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with diheptadecyl ketone in the presence ofhydrogen and a hydrogenation catalyst at aternperature of from aboutatmospheric to about 200 C.

6. The product resulting from the reductive alkylation of1,3-diamino-2-propanol with ethyl amyl ketone in the presence ofhydrogen and a hydrogenation catalyst at a 7. The product resulting fromthe reductive alkylation of 1,3-diamino-2-propanol with methyl ethylketone in the presence of hydrogen and a hydrogenation catalyst at atemperature of from about atmospheric to about 200 C.

References Cited by the Examiner UNITED STATES PATENTS 2,533,723 12/50Dombrow 260-566 temperature of from about atmospheric to about 200 C. 10CHARLES B. PARKER, Primary Examiner.

1. THE PRODUCT RESULTING FROM THE REDUCTIVE ALKYLATION OF1,3-DIAMINO-2-PROPANOL WITH A KETONE SELECTED FROM THE GROUP CONSISTINGOF ALIPHATIC KETONES AND CYCLOALIPHATIC KETONES IN THE PRESENCE OFHYDROGEN AND A HYDROGENATION CATALYST AT A TEMPERATURE OF FROM ABOUTATMOSPHERIC TO ABOUT 200*C.